DE1939015C3 - Acrylonitrile fiber and process for its manufacture - Google Patents

Description

different directions different friction methods to determine the »different

Furthermore, a method for the friction effect "is to be found in the" Journal of the

Position of this fiber. Textile Institute ", VoL 37, T 269 (1946). The fiber according to the invention is characterized by the height of the protuberances is at least

shows that the saponified outer layer of the fiber in 5 0.2 μ and is preferably between 0.3 and 1.0 μ.

Dimethylformamide is insoluble at 75 ° C and if the height of the protuberances is less than 0.2 μ, Cross-section less than 40% of the fiber cross-section then the grip of the fiber product will not be

is that the protuberances improved at a level of.

0.2 to 1.0 μ and at intervals of 1.5 to 12 μ The distance between the protuberances is in the range

the fiber surface and fold-like and _J0 between 1.5 and 13 μ, preferably between 1.5 and

surrounding the fibers discontinuously 12 μ, with again distances between 2.5 and 7 μ

where the borderline of the protube is preferred.

satchel at an angle of 75 to 105 ° to the fiber F i g. 5 shows the dependence of the distance dei

The axis runs protuberances from the grip of the knitted fabric.

The process according to the invention for the production i ₅ The starting material was obtained by spinning this fiber is characterized in that the ver of fibers, the protuberances of which have a height of soaping of the outer layer only up to an extent of 0.6 μ and distances between 1 and 12 μ exhibited, of less than 40% of the cross-sectional area of the fiber with no different frictional fiber and that the fiber showed effect after saponification. They were treated in opposite directions with a shrinkage agent, the ao yarn made from forty single threads, which then causes a greater shrinkage in a "right" knit pattern to a knitted fabric in the unsaponified area of the fiber than in the saponified outer 12 gauge . Area. The assessment of the grip has been made by many

The cross-section of the protuberances can be made in fiber-experienced test persons, and

Longitudinally symmetrical or asymmetrical, although the G iingk ^ .i was rated in five grades

drawn to the midline of the protuberances, run. divided, with a grip similar to that of

The prominences can also be discontinuous so that the cashmere wool conveyed feeling corresponds with 5

be arranged around the fiber so that the edge (best rating) and that of conventional acrylic

Boundary line of the protuberances under a nitrile fiber material without protuberances rated 1

Angle between 75 and 105 ° to the fiber axis. Turned 30. The term "discontinuous" is intended to be used here. 5 you can see that the grip of the

indicate that the majority of the protuberances are not in substance at intervals of the protuberances between

a completely closed circle around the fiber is 1.5 to 12 μ better than at distances of 1 μ

runs around, but that the cross-section according to which the effect of the protuberances is considerable

present invention is preferably asymmetrical 35 less and the feel of the fabric about dei

and that the direction of this asymmetry is the same as- a substance made of a fiber material without protuberance-

remains so that the fiber corresponds to a different tolerance. What is particularly interesting is that dei

exercise effect shows. optimal spacing of the protuberances with respect to the

F i g. 1 shows the outer layer with the best grip of the fabric that can be achieved according to the invention is 3 μ,

proper fiber; 40 is by far smaller than that of wool fibers.

F i g. 2 and 3 show electron microscopic, stepping distance, which is between 6 and 12 μ,

according to the scanning principle executed recordings according to the present invention has a fiber

Surface condition of a fiber according to the invention; material with different frictional effects F i g. 4 shows the relationship between the tuberances, the cross-section of which is along the fiber

resistance exerted by the f: iser when it is asymmetrical from its 45 axis, with the direction dei

the fiber bundle is pulled out, and the asymmetry coincides with the direction in which

draw distance; the fiber was drawn during manufacture. Dei

F i g. 5 shows the relationship between the frictional resistance when pulling it out

stand the individual protuberances on the fiber fiber from a fiber bundle in one of the teeth

Surface and the grip of a direction from the fiber 50 in the same direction (arrow direction in Fig. 3)

produced knitted fabric. was determined on different train routes, urr

The height, shape and spacing of the protuberances are shown in FIG. 4 curve shown to get ^. Ali

The maximum tensile resistance under the electron microscope was obtained from the second according to FIG. 4 dei

The recorded image is calculated, in which the tensile resistance value denoted by T _{x is assumed}

Fiber at right angles to the primary electron beam 55 which, when the fiber is withdrawn, moves in a dei

aligned and resulted in the focus on both sides of the fiber (upper toothing in the same direction,

and lower part in FIG. 2 or 3) chose. Friction was also separated from this

The phrase "different frictional effect" resisted pulling a fiber out of the

is used here to express that the fiber bundle moves in the opposite direction (against the ir

due to the interlocking of the fiber surface in the 60 F i g. 3 arrow direction) measured, unc

Pulling a fiber out of a fiber bundle with different pulling distances. As a maximum!

The resulting frictional resistance is greater when the tensile resistance was measured in the opposite direction

the fiber from the top end to the bottom end, i.e. tensile resistance T ₂ assumed. The ratio TJT

in one opposite to the interlocking of the fiber provides a measure of the different friction

Direction, pulling out of the bundle, as if one were 65 effect. According to the invention this ratio is!

it from the lower to the upper end, so in one of the TJT ₁ preferably between 1.3 and 3.5. The higher you

Toothing in the same direction from which the protuberances are, the smaller it is preferably » Pulls out bundle. Details on the measurement of this ratio were chosen. One difference

Lichen friction effect fiber leads to a further possible protuberances of a height of min-improved grip than a fiber material without at least 0.2 μ at intervals of 1 to 13 μ on the

this effect. Form fiber surface.

The production of the acrylonitrile according to the invention. The denaturation treatment of the fibers takes place fiber material is carried out by treating the fiber 5, preferably with an aqueous solution of alkali material from an acrylonitrile polymer with a hydroxide, alkaline earth metal hydroxide, sulfuric acid, Saponification or denaturing medium (becomes after chloric acid, nitric acid, hydrazine or hydroxyl defined) and then immersing the amine salts. Changed during this treatment treated fiber material in a shrinking medium the fiber structure from the outside to the inside. In detail, an acrylonitrile homo is stepping. Of course, other than the above can also be used polymer or an acrylonitrile copolymer, the denaturing media listed are used, forms from at least 85 percent by weight of acrylonitrile. and to produce a sufficient number of protuberances in a mono suitable for interpolymerization, mer, for example methyl acrylate, methyl methacrylate, if the area of the outer layer is less than 40%, Vinyl acetate, vinyl chloride, vinylidene chloride and vinyl-15 preferably less than 30% of the cross-sectional area bromide, is made using a wet or dry.

Spinning process or a dry and wet spinning process, the fibers are saponified or dehydrated or with the help of a spinning process, discolored when natured, then they can be used by users the materials are in a molten, acidic, or conventional bleach-like state, spun. »O can also be bleached using.

use the conjugate spinning process. The shrinkage treatment is carried out by means of rapid The acrylonitrile copolymer can be a basic medium suitable for heating the fibers with the aid of an inert heating copolymer formation or by immersing the fibers in a monomer such as acrylamide or vinyl pyridine or a glycol solution of an organic carbonate, acidic monomer such as sodium vinylbenzene sulfonate 95, which is a solvent for acrylonitrile, and an-sodium parasulfophenylmethallyl ether or sodium- heats the fibers, carried out containing methallylsulfonate in order to increase the dyeability. To achieve rapid heating, one can improve. For example, the fibers in an inert liquid bath. The fiber material is then immersed in water at a high temperature, or it can be washed with and stretched to align the molecules. 30 Steam or superheated steam or by touch stretched fibers can then be heated in a loose or with a heated metal surface, for example a tensioned state, a heat treatment under roller, or a plate, provided the fibers are drawn. The fibers are then present in the form of filaments, a saponification or denaturation medium. Glycol, for example, can act as an inert liquid. A "denaturing ethylene glycol, propylene glycol, diethylene glycol, gelling medium" used here means a chemical compound or polyethylene glycol, molten metal, which is used to make the outer layer of the or a hydrotropic medium such as urea or fiber insoluble for dimethylformamide at 75 ⁰ C to make thiourea, or a concentrated aqueous solution, and which also serves to structure the hydrotropic medium. Briefly, change of the outer layer compared to the fiber 40 said, for rapid heating, an inner layer process is created. Applied with the denaturing, which is suitable for the fibers approximately medium treated fibers are then subjected to a fast suspended or (e.g., within a minute) on heating medium to ereingetaucht a desired temperature above 130 ⁰ C in a solution containing warm at the same time as the shrinkage, in order to ensure that it is at least 5% too medium for shrinking the fiber. 45 shrink.

The fact that the protuberances develop has its main effect in that the structure of the Acrylnhril fiber heat (heat shock) are emphasized. With every dei by treatment with the saponification or examples listed below, no odei Denaturing medium, from its outer layer, only very weak protuberances are formed going inward to (middle class) is changed. 50 the fibers to the saponification or denaturation Here, the chemical and physical media are first exposed and gradually heated The typical properties of the outer layer changed by a shrinkage in the same order of magnitude If then the fibers undergo a quick heat treatment. Protuberances, the height of which is 0.2 μ excessively long are subjected to, for example, when one rises are only generated according to the invention <jie fibers an inert heating medium at 55 when the fibers are heated quickly. j exposed to high temperature or in a heated lo- As a glycol solution of an organic carbonate The solvent for the acrylonitrile polymer was immersed in ethylene glycol, diethylene glycol, glycerine or the like then the inner layer is stronger than the outer polyethylene glycol with a maximum of 30% ethylene carbonate shrunk layer propylene carbonate trimethylene carbonate tetramethy

The height and spacing of each protube- 60 carbonate or γ-butyrolactone used

dance through the conditions for the denaturation with the saponification or denaturation

ration and shrinkage treatment set Medium treated fibers are put into the glycol

Also, the conditions of the shrinkage treatment solution of the organic carbonate are immersed in

development is responsible for whether the cross-section is then ^{heated in the solution to over 70 0} C, so that si

Shrink protuberances symmetrically or asymmetrically by at least 5%. The warming came

runs and whether the fiber has a different tearing, but also after the fibers come out of the solution

exercise effect shows or not taken out and so strongly expressed

According to the present invention, it is without the amount of solvent remaining in the fibers

is a maximum of 300% of the fiber's own weight will.

Fibers that show a different frictional effect are produced by using the Saponification or denaturation medium treated fibers in an aqueous solution with a maximum of 30% an organic carbonate (solvent for acrylonitrile) such as ethylene carbonate, propylene carbonate, trimelhylene carbonate, Tetramethylene carbonate or γ-butyrolactone is immersed and they are in the solution up over 70 'C to shrink them by at least 5%. The heating process can also after the Fibers were taken out of the solvent and expressed so strongly that only maximally 200%, based on the own weight of the fiber of the solvent, the fiber adhering, made will.

The aqueous solution of an organic carbonate can be a neutral salt, preferably alkali sulfate, Contain alkaline earth sulphates, manganese sulphate, aluminum sulphate or ammonium sulphate. If you add these salts to the aqueous solution, then you can reduce the concentration of the organic carbonate. Adds if, for example, sodium sulfate is added, then it is possible to increase the concentration of the ethylene carbonate decrease by a third. The aqueous solution of the organic carbonate can be a plasticizer for contain the conventional fiber material made of acrylonitrile. If you add such a plasticizer, then it is possible to forego the softening treatment. This procedure is then appropriate, when the shrinkage treatment is carried out on the yarn or the knitted fabric or the woven fabric. at Such a procedure prevents the grip of the fiber material according to the invention and the conventional acrylic membrane fiber material produced by the mutual Adhesion of the conventional fibers in the shrinking treatment is deteriorated.

The heat shrinkage treatment can be performed with practically no tension or with little tension can be carried out in any processing state, for example on the cable, on staple fibers, on spun yarn or on fabrics. Furthermore, similar protuberances can then also be produced when considering the denaturation treatment and the heat shrinkage treatment in different Performs procedural stages. For example, if the saponification or denaturation of the Fibers in the form of cables, then the cables are spun into yarns and then the heat shrink treatment on the yarn.

Another object of the present invention is to provide a method by which is to produce a fiber article of remarkably high commercial value. The inventive Fiber delivers a product which, due to its prominences, is soft, wool-like and greasy shows a highly elastic grip, similar to that of a fiber material made of wool of good quality. LYes the Protuberances suppress displacement of the fiber in the product, but in the case of the invention Fibers are not as sharp as with WoHe, the product shows a phenomenal reduction the pill addiction which is just a downside acr Is wool products. _,

According to one embodiment of the present invention, it is possible to initially only have one basic Dye-dyeable acrylonitrile fibers can now also be dyed with acidic dyes.

The fiber according to the invention, having the properties mentioned, is preferably used together with other types of fiber, for example wool, cotton, rayon or acrylonitrile fibers, polyester fibers and polyamide fibers, spun, twisted, knitted and woven. For example, it is possible to use the pill propensity of wool to decrease even more without

ίο their excellent grip deteriorate, though the fiber according to the invention is spun together with wool. So it is possible to produce a product of extraordinary high commercial value. It also arises when spinning together

t ₅ of the inventive fiber, because the fiber of the invention with a basic dye and wool with an acid dye is dyeable together with wool a multi-color effect.

example 1
ao

An acrylonitrile copolymer with 92% acrylonitrile and 8% vinyl acetate is in dimethylacetamide dissolved to produce a spinning solution with a 28% concentration of the polymer. The spinning solution is passed through a spinneret into a coagulation bath of 50% dimethylacetamide kept at 40 ° C and 50% water pressed to form filaments. The filaments are in boiling water stretched to 4.5 times its length, washed with water, dried at 140 ° C. and then by means of Heat treated steam at a pressure of 2.5 kg / cm * in a loose state.

The cable produced contains mono-filaments having a denier of 3, the total denier is 60 000. The cable is immersed in a maintained at 90 ⁰ C 2 _"o aqueous sodium hydroxide solution for 30 minutes to saponify the outer layer of the fiber , then it is bleached with the help of a 2% aqueous oxalic acid solution at 98 ° C for 15 minutes.

The fibers of the cable are wrapped in a paraffin and

Embedded and containing ethyl cellulose substance cut into a slice 4μ thick. This section is dipped in dimethylformamide to dorl to be partially solved.

F i g. 1 shows an electron microscope image (electron microscope Type JSMII manufactured by Japan Electron Optics Laboratory Co., Ltd.) of un soluble part of the cut. From Fig. 1 is zi see that the insoluble part in thickness of 1 μ au! the fiber surface has been formed.

However, such an insoluble part does not arise on a fiber which does not contain an aqueous sodium Hydroxide solution has been treated.

In the present example, the ratio of the area of the outer layer to the cross-sectional area is the fiber 21%.

The cable treated with aqueous sodium hydroxide solution is continuously shrunk to a given value in a Glykofbad, as listed in Table 1, while the! Train is monitored. After washing with water, the aftertreatment takes place.
F i g. 2 shows the surface condition of the fiber produced. The recognizable fold-like protuberances show an edge delimiting film which runs at an angle between 75 and 105 ° to the fiber axis

The protuberances surround the fiber surface discontinuously.

The distances and the height of the protuberances are different, depending on the shrinkage process existing conditions (see table 1).

10

For comparison, fibers which have not been subjected to any treatment in a sodium hydroxide solution are used have also been subjected to a shrinkage treatment. However, none are formed Prominences.

table

Shrinkage medium temperature Shrinkage in Prolneranzen distance height No. of shrinkage
bath (μ) (μ) <· /
/O 50 1 0 Ethylene glycol ("C) 25th 6.0 0.5 1 Ethylene glycol 180 18th 3.0 1.0 2 Glycerin 180 37 5.5 0 7 3 Glycerin 200 20th 6.4 0.8 4th Glycerin 200 25th 9.4 0.4 5 Glycerin 180 18th 10.1 0.3 6th Propylene glycol 180 15th 9.5 0.4 7th Polyethylene glycol 180 15th 8th 180

Fiber length before shrinkage - fiber length after shrinkage

Shrinkage (%) = - _, - ■ ■

Fiber length before shrinkage 100

The fibers produced in this example are soft, fun and soft, greasy and elastic

greasy and highly elastic. You are knitted to make 30 pieces of knit fabric. The properties of the

very suitable for knitted fabrics and fabrics. tenen fabric and the fabric from the conventional

Fibers of No. 3 in Table 1 are combined in stacks of acrylonitrile fibers in Table 2

medium length of 100 mm and divided into the same yarn with the values 2/36 MC (185/320 T / M) ver

table

Fabric made from # 3 fibers
in table 1

Fabric made from a conventional fiber material

Elasticity against compression

85.3 79.5

Compression elasticity: Measurement is carried out according to JIS-L-1005 standard.

Anti-pill tendency: Classification is based on the changed appearance of the fabric surface after processing with a drum tester (manufactured by Atlas Electric Device Co.) in accordance with JIS-L-1018-1962 standard. (The higher the rating number, the lower the tendency to pill.)

Grip: The evaluation is based on tactile tests carried out by several in the determination of the Skid resistance is carried out under the assumption that the skid resistance of an experienced test is not carried out according to the present invention treated fibers manufactured with the numeral 1 and a from Merino wool product is rated with the number 5.

Example 2

A cable made of acrylonitrile fibers, which were produced in the same way as described in Example 1, is treated with a 57 ″ aqueous Anli-Pill-Ne: supply which is kept at 80.degree
(Degree)

4 to 5
3 to 4

grip
(Degree)

3, «
1.0

Treated sulfuric acid solution for 10 minutes, then washed out with water and dried.

The fibers obtained have a dimethyl form-

amide-insoluble outer layer as in example 1. The ratio of the outer layer area to the fiber cross-sectional area is 18%.

The cable is then converted into urea as a hydrotropic Medium or in molten metal of the

Composition bismuth 50%, lead 24%, tin 14 " _or cadmium 12% immersed at a temperature of 17t) ⁰ C in order to shrink.

runs at an angle to the fiber axis.

Example 3

Example 1 is repeated with the difference that the conditions listed in Table 3 in the Heat shrinkage process can be applied. One can observe that on the fiber surface Form protuberances that run approximately at right angles to the fiber axis.

As reference examples, do not use sodium hydroxide solution treated fibers also correspond to one of the conditions listed in Table 3 Subjected to heat treatment without protruding crowns form on the fiber surface. The fibers tend to be partially in the shrinkage medium loosen and glue together so that they are not weiierverarbeilel in the usual way be able.

Table 3

Shrinkage medium Shrinkage conditions time temperature (Minutes) (Parts by weight) ( ⁰ C) Ethylene carbonate / 15th Ethylene glycol (25/75) .. 100 Ethylene carbonate / 30th Glycerine (20/80) 100 Propylene carbonate / 10 Ethylene glycol (25/75) .. 100

Example 4

Example 1 is repeated with the difference that the conditions listed in Table 4 in the Heat shrinkage treatment can be applied. The surface of the fiber obtained in this way is in F i g. 3 shown. The formed on the fiber surface

Deten protuberances differ quite considerably from those which are obtained by proceeding according to Example 3. The cross-section of the protuberances along the fiber axis is asymmetrical to the center line of the protuberances, and ^d: e direction of the asymmetry of the cross section is constant. The height and the spacing of the protuberances with an asymmetrical cross-section change with the shrinkage conditions.

ίο In F i g. 2 and 3, the arrow direction shows the squeezing direction the dope in the manufacture of the fiber. As a reference example, an in Dimethylformamide insoluble substance coated fibers under the conditions listed in Table 4

iS shrunk to form protuberances, which show no different frictional effect. From this it can be understood that the formation of Protuberances with an asymmetrical cross section depends on the deformation process.

ao A cable produced according to the present example is loaded in a measuring arrangement with the dimensions 5 × 5 × 10 cm with a weight of 33 g / cm ² and the tensile resistance of the fiber from the fiber cable is measured at a tensile speed of 160 cm / min. The frictional force, which corresponds to a maximum tensile resistance in or against the direction of the fiber interlocking, is listed in Table 4. It goes without saying that protuberances which show such a different frictional effect are not produced in fibers which do not have a special outer layer even after a heat shrinkage treatment.

Table 4

Shrinkage medium Shrinkage conditions time
(Minutes) Train towards Frictional force shrinkage No. (Weight percentage) temperature
CC) 15th UCI Γ UaC-I ~
gearing (G)
Train in counter
direction of % Ethylene carbonate / water 90 3.5 fiber
gearing 20th 9 (20/80) 30th 6.6 Gamma butyrolactone / 90 3.4 15th 10 _ Water (25/75) 15th 5.5 Ethylene carbonate / 95 3.2 28 11th Sodium sulfate / water 7.5 _ (6/44/50) 30th Ethylene carbonate / 95 4.0 21 12th Magnesium sulfate / water 7.6 _ (10/39/51) 15th Ethylene carbonate / 95 3.7 19th 13th Manganese sulfate / water 7.0 (7/59/34)

The fibers obtained according to the present example show protuberances, the cross section of which is along the The fiber axis runs asymmetrically, the direction of the asymmetry being constant.

The fibers are softer and more woolly fat than the fibers according to Example 1. The one from the The fabric made from fibers of this example received a hand grip rating of 4.2.

Example 5

A cable made of acrylonitrile fibers, produced according to the method described in Example 1, is with an aqueous solution of a saponification or Denaturierungsmedhims, which in Table 5 is listed, treated to the fiber outer layer linifislirVi in nimptlivTfnrmamiil m

do. The ratio of the area of the outer layer to the fiber cross-sectional area is also in Table 5 listed.

The cable is then ^{kept at 90 °} C. in an aqueous solution of

Ethylene carbonate with 20 parts by weight of ethylene carbonate and 80 parts by weight of water 30 minutes Long treated Here, protuberances are formed on the fiber surface, which differ from one another Show frictional effect.

Table 5

Saponification resp.
Denaturation medium

Saponification resp.
Denaturation conditions

Concentration of the medium temperature
( ⁰ C)

time
(Minutes)

Ratio of the outer layer to the other

Sodium hydroxide
Potassium hydroxide.
Lithium hydroxide

1.5 3fi

15 95
95

95

30th 30th 30th

17 13 15

Example 6

An acrylonitrile copolymer made from 92.5% acrylonitrile, 7% methyl acrylate and 0.5% sodium sulfophenylmethallyl ether is dissolved in dimethylacetamide to make a spinning solution.

This spinning solution is pressed into a coagulation bath to form filaments. The filaments will stretched, washed, dried and a heat treatment by means of steam in the same way as in Example 1 described subject.

The fibers obtained are divided into stacks with an average length of 100 mm and heated at 120 "C in a bath containing 13 weight percent hydroxylamine sulfate and 20 weight percent sodium phosphoric acid in a bath ratio of 1: 7 90 minutes treated, then washed out with water and dried.

The resulting fibers have an outer layer that is insoluble in dimethylformamide as well as in Example 1. The ratio of the outer layer area to the fiber cross-sectional area is 29%.

The fibers are then treated with a 20% aqueous solution of ethyl carbonate at 95 ° C. for 30 minutes treated to shrink. After that, the fibers show protuberances on the fiber surface, which show a different frictional effect, as shown in Table 4.

The fibers obtained can be dyed with an acid dye. The ones generated according to this example Fibers are used together with the fibers listed under No. 11 in Table 4 in a ratio 25:75 in counter-rotating yarn of 2/36 MC (250/360

T / lvi) and then spun in a "right" knit pattern knitted in a 14 gauge knit fabric and dyed under the following conditions:

C. 1. Acid Yellow 25 .. 1.2 weight percent

C. I. Basic Yellow 25 .. 0.2 weight percent

C. I. Basic Red 29 2.0 weight percent

C. 1. Basic Blue 54 0.3 weight percent

Sulfuric acid 0.5 percent by weight

Bath ratio 1:30

Temperature 100 ⁰ C

Time 60 minutes

The fabric dyed in this way shows multicolor due to the yellow acid dye and of the light brown basic dye. The product has very high commercial value as a result of it soft, greasy and elastic properties.

The color fastness is determined to be excellent in a JIS (Japanese Industrial Standard) test (see table 6).

For comparison, a fiber material treated only with hydroxylamine sulfate is used together with the conventional one Acrylonitrile fiber material and the resulting yarn spun under the same conditions colored as described above. The properties of the fabric obtained are also shown in Table 6.

table

Color fastness (class)

Color fastness to light

MC-2 ¹ )

Discoloration,

Fading spots

MC-2 ² )

Discoloration,

fading

stains

Washability ³ ) dry | well

Dyed fabric, manufactured
according to the present
example

Dyed fabric, manufactured
for comparison

5 to 6 5 to 6 to 5
until 5

4 to 5
4 to 5

4 to 5 4 to 5

resistance
gigen AnU-PiB- Grippy Together Tilt speed to press*) (Degree) (Degree) Dyed Fabric, here represents according to before lying example 89.4 4 to 5 4.4 Dyed Fabric, here provides for comparison 30.6 3 to 4 1.5

i) test according to

») Check according to

') Test according to JISLlOWWS ^ N

«) Test according to JIS-L-1005-Νοπη.

Example 7

An acr / nitrile copolymer with 95% acrylonitrile and 5% acrylamide is used to produce a Spinning solution dissolved in dimethylacetamide

The spinning solution is introduced into the precipitation bath in order to form filaments which, as in Example 1 described stretched, washed, dried and subjected to a heat treatment with steam.

The obtained fibers are cut in fiber stack an average length of 100 mm and in a bath containing 20 percent by weight of hydrazine and a bath ratio of 1: treated for 90 minutes at 100 7 ⁰ C, then washed with water and dried. The fibers obtained have an outer layer which is insoluble in dimethylformamide, like the fiber described in Example 1. The ratio of the outer layer area to the fiber cross-sectional area is 16%.

The fibers are then treated in a bath with 8 parts by weight of ethylene carbonate, 42 parts by weight of sodium sulfate and 50 parts by weight of water at 98 ⁰ C for 30 minutes to shrink. The fibers obtained show protuterances on their surface, in which a different friction effect can be determined.

Example 8

Conventional acrylonitrile fibers with an average length of 100 mm and 3 denier are spun into a multifilament yarn of 36 MC (250/360 T / M) using the conventional worsted spinning process. The yarn obtained is treated at 90 ⁰ C for 30 minutes in a 2% aqueous sodium hydroxide solution, and then bleached with a 2% aqueous oxalic acid solution at 98 ° C for 15 minutes. The ratio of the outer layer area to the fiber cross-sectional area is 21%.

The yarn is then immersed for 10 minutes in a maintained at 40 ⁰ C 7% aqueous Äthylenkarbonatlösung, then so strongly expressed from this solution is removed and that the remaining solution to the yarn accounts for 70 percent by weight of the yarn. The yarn is then ^{dried at 100 °} C. for 60 minutes in a drying device using hot air.

The cross-section of the

The protuberances formed run asymmetrically along the fiber axis, the direction of the asymmetry being constant

Example9

The same acrylonitrire polymer fibers as in Example 8 are used in a 13 weight percent bath Hydroxylamine sulfate and 20 percent by weight sodium phosphate and a bath ratio of 1: 7

ίο 120 ⁰ C for 90 minutes treated long, then washed with water and dried The fibers obtained have an outer layer insoluble in dimethylformamide as the fibers obtained in Example. 1 The ratio of the outer layer area to the fiber cross

Cut area is 25%.

The fibers are in a 40:60 ratio with conventional 3 denier acrylonitrile fibers multi-thread yarn of 36 MC (250/360 T / M) is spun and the resulting yarn is

»O standing conditions colored:

C. I. Acid Yellow 25 .. 1.7 weight percent C. I. Basic Yellow 25 .. 0.2 weight percent C. I. Basic Red 29 2.0 weight percent

₉ . CI Basic Blue 54 0.3 percent by weight

Sulfuric acid 5.0 percent by weight Bath ratio 1:30 Temperature 100 ⁰ C Time 60 minutes

The dyed yarn is then placed long in a suspension of 8% ethylene carbonate, 7% plasticizer and which is maintained at 40 ⁰ C 85% water, 10 minutes, and then as strong words, that the remaining on the yarn weight suspension 7 percent of the yarn is then the yarn at 12O ⁰ C for 60 minutes dried in a drier using hot air. As a result, protuberances are formed on the surface of the fibers obtained, which one below different friction effect, as shown in Table 4 is led, show.

The yarn comes in a »right-knit pattern with 14 gauge knitted The dyed knitted fabric is multicolored, namely yellow due to the acid dye and light brown due to the basic dye. Its commercial value is very high as a result of its very soft, greasy and elastic properties.

Example 10

An acrylonitrile copolymer (component A) with 95% acrylonitrile and 5% vinyl acetate and a Acrylonitrile copolymers (B component) made from 91.5% acrylonitrile and 8.5% vinyl acetate are used in Dimethylacetamide to create a spinning solution dissolved with a concentration of the polymer of 23.5% in each case. Both spinning solutions are simultaneously by common adjacent openings in a 1: 1 ratio in a bath maintained at 3O ⁰ C coagulation bath with 60% dimethylacetamide pressed to form conjugate filaments, which are stretched in boiling water to 5 times their length and then ^{dried at 140 0} C and constant length. They then undergo a heat relaxation treatment under the action of a saturated steam of 2.0 kg / cm * pressure to a shrinkage of about 20% achieve. This creates a ripple. The conjugate fibers obtained, whose mono-

Filaments have a denier value of 3, stacks with an average length of 100 mm are cut, treated with a 2% aqueous sodium hydroxide solution kept ^{at 90 °} C. for 30 minutes and then with a 3% aqueous acetic acid kept ^{at 90 ° C. for 30 minutes} bleached The fibers obtained are then placed in a ^{glycerine bath previously heated to 180 °} C. in order to shrink quickly. at

this treatment are formed on the fiber surface Protuberances, the margin of which runs approximately at right angles to the fiber axis.

The fibers obtained are then combined with merino wool in a ratio of 80:20 gSfafigeGani of 36MC (185/320 T / M) ran out and knitted very soft, greasy and elastic.

1 sheet of drawings

Claims (10)

indicates that the aqueous solution contains a plasticizer. Claims: -q Method according to one of Claims 6 to 1O1, characterized in that the 1. Fiber from an acrylonitrile homopolymer 5 Schnimpfungsmedium treated fiber then. or from a copolymer with at least ßend undocked and then to a temperature 85 percent by weight polymerized acrylonitrile, heated above 70 C. whose outer layer is saponified and the one on the Fiber surface has protuberances, there characterized by that the ver io soaped outer layer of the fiber is insoluble in dimethylformamide at 75 ° C and its cross-section is less than 40% of the fiber cross-section,. . that the protuberances at a height of 0.2 to The invention relates to a fiber made of an acrylic 1.0 μ and at intervals of 1.5 to 12 μ on the nitrile homopolymensate or from a mixed poly fiber surface and are wrinkled and the merisate with at least 85 percent by weight of polymer fiber is discontinuous surrounding it, sated acrylonitrile, the outer layer of which is saponified wherein the edge delimitation line of the protuberances and the protuberances on the fiber surface point at an angle of 75 to 105 ° to the fiber axis. Furthermore, the invention relates to a course, ao drive for the production of this fiber. 2. Fiber according to claim 1, characterized in that fiber materials from an acrylic are characterized by the fact that the cross-section of the protuberances nitrile polymer due to their good physical properties along the fiber axis is asymmetrical to the center line to a large extent for the production of the protuberances and that the fiber of knitted and woven fabrics used, but material a different frictional effect »5 there are still some consumers who this _ze igt. Do not appreciate material as it is different from a 3. A method for producing a fiber according to material made of natural fibers to the touch of the fiber claim 1 or 2, in which the outer layer of a material made of an acrylonitrile polymer in relation Fiber made from acrylonitrile homopolymer or from this referred to below as "grip" resemble a mixed polymer with at least 85% properties of a material made of natural fibers, weight percent polymerized acrylonitrile saponified, many attempts have already been made is characterized in that the saponification has so far always been without 100% success. So one has the outer layer tries only to the extent of, for example, the curl characteristics less than 40% of the cross-sectional area of the fiber material made of an acrylonitrile polymer Fiber takes place and that the fiber after the 35 through application of the conjugate spinning process soaps treated with a shrink agent or similar processes to improve is that in the unsaponified area of the fiber that it receives a wool-like feel. It has causes greater shrinkage than in the saponified but shown that it is not enough, only that outer area. Crimping properties of the acrylonitrile polymer fiber 4. The method according to claim 3, characterized thereby to improve 40 in order to give it an elastic, soft, wool-like drawing that the saponification agent to impart an aqueous greasy grip. Solution of an alkali hydroxide, an earth- A good quality wool fiber points to their alkali hydroxide from sulfuric acid, from the hydroxyl surface protuberances, which here as »ver amine salts or hydrazine. zahnung «. These affect the 5. The method according to claim 3, characterized marked 45 fiber processing and are for the grip of the indicates that a product is decisive as a shrinkage medium. The conventional acrylic liquid, which is kept at least 130 ° C and formed by nitrile polymer fibers, does not show any such from glycols or hydrotropic media or me- protuberances. fall of a lower melting point, is selected. By U.S. Patents 3,124,413 and 6. The method according to claim 3, characterized in that 50 3 127 233 it has become known, polyacrylonitrile that is used as a shrinkage medium to treat fibers with alkali hydroxides. This Organic carbonate treatment kept at least 70 ° C is used to improve the coloring properties of Solution is used to change the solvent for acrylic fibers. Acrylonitrile similar to natural fibers is suitable. Licher grip cannot be achieved in this way. 7. The method according to claim 6, characterized in that 55 The same applies to the Belgian patent draws that an aqueous Lö- fonts 546 321 and 403 505 known versification of an organic carbonate is used as the carbonate solution. drive that a treatment of polyacrylonitrile fibers 8. The method according to claim 6, characterized or synthetic fibers generally by means of an aqueous indicates that the carbonate solution is a glycolic hydroxylamine solution or other bases, solution of an organic carbonate used 6 »Finally, the treatment of acrylic is also used. threads with organic carbonate solutions and others 9. The method according to claim 7, characterized in that swelling agents according to the Belgian patent are characterized in that the aqueous solution contains a sulphate 607 552 and no such change in the threads holds, which of sodium sulfate, potassium sulfate, cause that the desired handle is achieved. Magnesium sulfate, zinc sulfate, aluminum sulfate, 65 The invention is based on the object of providing a Manganese sulfate or ammonium sulfate is selected to create acrylonitrile fiber by its structure a grip is achieved that is that of a fiber 10. The method according to claim 7, thereby corresponding wool of good quality and the one in different